CN110350184B - Preparation method of high-capacity NiMoO4 energy storage material for battery positive electrode material - Google Patents

Preparation method of high-capacity NiMoO4 energy storage material for battery positive electrode material Download PDF

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CN110350184B
CN110350184B CN201910560427.XA CN201910560427A CN110350184B CN 110350184 B CN110350184 B CN 110350184B CN 201910560427 A CN201910560427 A CN 201910560427A CN 110350184 B CN110350184 B CN 110350184B
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nickel
hydrothermal reaction
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nimoo
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卢锡洪
周丽君
曾思琪
郑得洲
徐维
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Wuyi University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/24Alkaline accumulators
    • H01M10/30Nickel accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention relates to a high-capacity NiMoO for a battery anode material4The preparation method of the energy storage material comprises the steps of synthesizing nickel metal organic framework Ni-MOF through a first hydrothermal reaction by taking organic acid and a nickel source as precursors, DMF as a solvent and foamed nickel as a substrate; then putting the obtained Ni-MOF sample into a reaction kettle filled with mixed precursor liquid consisting of polyvinylpyrrolidone, a nickel source, a molybdenum source and deionized water, carrying out secondary hydrothermal reaction, washing with distilled water, and drying to obtain NiMoO4An energy storage material. The preparation method is simple, low in energy consumption and environment-friendly, and the prepared material has good electrochemical performance, provides a good anode material for the existing nickel-zinc battery, and has great application prospects. The conductivity and the ion diffusion rate of the electrode material are improved by regulating and controlling the concentration of nickel nitrate, the concentration of sodium molybdate, and the temperature and time of the secondary hydrothermal reaction, so that the capacity and the stability of the electrode material are improved.

Description

High-capacity NiMoO for battery anode material4Preparation method of energy storage material
Technical Field
The invention relates to the technical field of energy storage materials, in particular to a method for synthesizing high-capacity NiMoO by taking nickel metal organic framework Ni-MOF as a substrate4A preparation method of the material used as the anode material of the nickel-zinc battery.
Background
Energy is an important basic resource for the development of human society, but with the rapid increase of the world population and the continuous development of the human society, the world energy demand is continuously increased, the traditional fossil energy cannot meet the requirement of the future society for energy for a long time, and the excessive development and utilization of the traditional fossil energy also aggravate the environmental pollution and increase the environmental protection pressure. Therefore, research and development of new efficient and stable electric energy storage devices to realize deep development and efficient utilization of energy are important research directions of energy storage technology at present.
Lithium Ion Batteries (LIBs) have attracted considerable attention over the past few decades due to their high cycle stability and high energy density. However, the safety problem and the resource limitation problem of lithium and cobalt greatly limit the further development of lithium ion batteries. It is appreciated that water-based rechargeable batteries, which have the advantages of high safety, low cost, abundant sources, environmental protection, etc., are receiving increasing attention. Among various water-based rechargeable batteries, nickel-zinc (Ni// Zn) batteries are considered to be a promising substitute product because of their advantages such as high discharge voltage (1.8V), large capacity, high safety, abundant resources, and low cost. However, the further widespread use of Ni// Zn cells is limited by the inevitable formation of negative zinc dendrites and poor cycle stability due to the irreversibility of nickel-based positive electrodes, as well as the low capacity of nickel-based positive electrode materials. In order to overcome this bottleneck, it is critical to find a nickel-based cathode material with high performance.
In recent years, ternary metal oxides having two different metal ions have received much attention due to their rich redox reactions and high electronic conductivity. For example, some ternary metal molybdates, e.g. MnMoO4、CoMoO4And NiMoO4Has been favored by more and more researchers over the past few years. Wherein, due to the high electrochemical activity of nickel ions, NiMoO4Is expected to become an ideal electrode material of high-performance super capacitors and batteries. Although NiMoO of different structures have now been developed4The preparation method is used for energy storage application, but the application of the preparation in the energy storage field is still limited due to poor conductivity.
Thus, NiMoO is improved4The conductivity of the material is the key to further improve the electrochemical performance of the material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for synthesizing high-capacity NiMoO by taking nickel metal organic framework Ni-MOF as a substrate4A preparation method of the material used as the anode material of the nickel-zinc battery.
The technical scheme of the invention is as follows: high-capacity NiMoO for battery anode material4The preparation method of the energy storage material comprises the steps of taking organic acid and a nickel source as precursors, taking N-N-Dimethylformamide (DMF) as a solvent and taking foamed nickel as a substrate, and synthesizing the materials through a first hydrothermal reactionA nickel metal organic framework Ni-MOF; then putting the obtained Ni-MOF sample into a reaction kettle filled with mixed precursor liquid consisting of polyvinylpyrrolidone (PVP), a nickel source, a molybdenum source and deionized water, carrying out secondary hydrothermal reaction, washing with distilled water, and drying to obtain the NiMoO4An energy storage material.
Further, the concentration of the organic acid is 0.05mol L-1The organic acid is one or a mixture of more of terephthalic acid, trimesic acid and phthalic acid.
Preferably, the organic acid is terephthalic acid.
Further, the nickel source is one or a mixture of nickel nitrate, nickel chloride and nickel sulfate.
Preferably, the nickel source is nickel nitrate.
Further, the concentration of the molybdenum source is 0.05-0.15 mol L-1The molybdenum source is one or a mixture of sodium molybdate and ammonium molybdate.
Preferably, the temperature of the first hydrothermal reaction is 100 ℃, and the time is 8 h; the temperature of the second hydrothermal reaction is 120-180 ℃, and the hydrothermal reaction lasts for 3-9 hours; the drying temperature and time are respectively 60 ℃ and 10 h.
Further, the average molecular weight of PVP is 24000, and the concentration is 1.5mmol L-1
Further, the concentration of the nickel source in the first hydrothermal reaction is 0.05mol L-1(ii) a The concentration of the nickel source in the precursor solution of the second hydrothermal reaction is 0.05-0.15 mol L-1
Preferably, the concentration of the nickel source in the first hydrothermal reaction is 0.05mol L-1(ii) a The concentration of the nickel source in the precursor solution of the second hydrothermal reaction is 0.1mol L-1
Further, the method specifically comprises the following steps:
s1), sequentially immersing the foamed nickel in acetone and 3mol L of foamed nickel-1Ultrasonic cleaning with hydrochloric acid and ethanol for 10min, 5min and 5min, respectively, and placing in a hydrothermal reaction kettle;
s2), the concentration is 0.05mol L-1And 0.05mol L of an organic acid of (2)-1Dissolving the molybdenum source in a DMF solvent, stirring until the molybdenum source is completely dissolved, pouring the solution into the reaction kettle in the step S1), reacting for 8 hours in an oven at 100 ℃, taking out, washing by distilled water, and drying at 60 ℃ to synthesize a Ni-MOF sample;
s3), placing the Ni-MOF sample in a container with L of 1.5mmol-1PVP、0.05~0.15mol L-1Nickel source, 0.05-0.15 mol L-1Carrying out a secondary hydrothermal reaction in a reaction kettle of a mixed precursor solution consisting of a molybdenum source and deionized water, washing with distilled water, and drying at 60 ℃ for 10h to obtain the NiMoO4An energy storage material.
The invention has the beneficial effects that:
1. the invention improves the conductivity and the ion diffusion rate of the electrode material by regulating and controlling the concentration of nickel nitrate, the concentration of sodium molybdate, and the temperature and time of the secondary hydrothermal reaction, thereby improving the capacity and the stability of the electrode material. By setting the optimal preparation conditions, the NiMoO with high electrochemical performance is obtained4An electrode material;
2. the preparation method is simple, low in energy consumption and environment-friendly, and the prepared material has good electrochemical performance, provides a good anode material for the existing nickel-zinc battery, and has great application prospect.
Drawings
FIG. 1 shows NiMoO prepared in examples 1 and 2 of the present invention4Scanning Electron Microscope (SEM) images of the energy storage material; wherein a is the NiMoO prepared in example 24Scanning Electron Microscope (SEM) image of high power and low power of energy storage material; b is the NiMoO prepared in example 14Scanning Electron Microscope (SEM) images of the energy storage material;
FIG. 2 shows NiMoO prepared according to examples 1 and 2 of the present invention4An X-ray diffraction (XRD) spectrum of the energy storage material;
FIG. 3 shows NiMoO prepared according to examples 1 and 2 of the present invention4The energy storage material electrode is 6mol L-1Sweeping speed in KOH solution of 10mV s-1Cyclic voltammetry curve;
FIG. 4 shows NiMoO prepared according to examples 1 and 2 of the present invention4Current density of energy storage material electrodeThe degree is 25mA cm-2A lower constant current charge-discharge curve;
FIG. 5 shows NiMoO prepared according to examples 1 and 2 of the present invention4Electrochemical impedance spectroscopy of the energy storage material electrode;
FIG. 6 is a NiMoO of the invention prepared in examples 1 and 24Rate capability of the energy storage material electrode;
FIG. 7 shows NiMoO prepared according to examples 1 and 2 of the present invention4The current density of the energy storage material electrode is 25mA cm-2Constant current charging and discharging stability.
Detailed Description
The following further describes embodiments of the present invention with reference to the accompanying drawings:
example 1
High-capacity NiMoO for battery anode material4The preparation method of the energy storage material comprises the following steps:
s1), immersing the foamed nickel of 2cm multiplied by 3cm in acetone and 3mol L in sequence-1Ultrasonic cleaning with hydrochloric acid and ethanol for 10min, 5min and 5min, respectively, and placing in a hydrothermal reaction kettle; then the concentration is 0.05mol L-1Terephthalic acid and 0.05mol L-1Dissolving nickel nitrate in a DMF solvent, stirring until the nickel nitrate is completely dissolved, pouring the mixture into the hydrothermal reaction kettle, reacting for 8 hours in a drying oven at 100 ℃, taking out, washing by distilled water, and drying at 60 ℃ to synthesize a Ni-MOF sample;
s2), taking the Ni-MOF sample obtained in the step S1), placing the sample with the size of 2cm multiplied by 3cm in a container filled with L of 1.5mmol-1PVP、0.05~0.15mol L-1Nickel nitrate, 0.05-0.15 mol L-1Carrying out a secondary hydrothermal reaction in a reaction kettle of a mixed precursor solution consisting of sodium molybdate and deionized water, washing by distilled water, and drying at 60 ℃ to obtain the NiMoO4Energy storage material, denoted as NiMoO4-2。
Example 2
To be sequentially immersed in acetone and 3mol L of-1NiMoO synthesized by step S2) of example 1 using foamed nickel as a substrate, which was ultrasonically cleaned in hydrochloric acid and ethanol for 10min, 5min, and 5min, respectively4The energy storage material is NiMoO4-1。
Performance analysis:
for NiMoO4-1 and NiMoO4-2 field emission scanning electron microscopy tests carried out on the electrode material, the results being shown in FIGS. 1 (a), (b), the scanning electron microscopy images showing the synthesis of NiMoO on two different substrates4All are nanowire materials, and an X-ray diffraction test is adopted in figure 2, which shows that the electrode materials prepared and synthesized on the two substrates are NiMoO4. FIG. 3 uses cyclic voltammetry in an electrochemical method, and FIG. 4 uses a constant current charge and discharge test in an electrochemical method to study the capacitance performance (6 mol L electrolyte solution)-1KOH) and calculating to obtain NiMoO synthesized by taking Ni-MOF as a substrate4At a current density of 25mA cm-2The specific capacitance of the area is 0.59mAh cm-2Is NiMoO directly synthesized by taking NF as a substrate under the same current density43.9 times (0.15mAh cm)-2) (ii) a FIG. 5 is an electrochemical impedance test, according to electrochemical impedance spectroscopy, NiMoO4The conductivity and the ion diffusion rate of-2 are obviously higher than those of NiMoO4-1 electrode material. FIG. 6 is a NiMoO4-1 and NiMoO4-2 rate capability of the energy storage material electrode. FIG. 7 shows the lifetime performance of the electrochemical device, which was determined by calculation using constant current charge/discharge test in the electrochemical method4-2 at a current density of 25mA cm-2After 2000 times of cyclic charge and discharge, the capacity retention rate still remains 85.5%, and NiMoO under the same current density4-1 the capacity retention is only 45.5% after the same cycle. These show the Ni-MOO based synthesis of NiMoO4The electrode material has excellent energy storage performance, which promotes the further development of the nickel-zinc battery to a certain extent.
Examples 3 to 10
The methods of examples 3-10 are the same as example 1, and based on the protocol of example 1, the NiMoO is influenced by controlling the concentrations of the secondary hydrothermal precursors (nickel nitrate, sodium molybdate) and the reaction temperature and time4The relationship between the properties of (A) and (B) is shown in Table 1.
TABLE 1 NiMoO4Regulation and control of secondary hydrothermal reaction
Figure BDA0002108093110000041
Figure BDA0002108093110000051
Examples 1, 3 and 4 and examples 1, 5 and 6 illustrate the concentration of nickel nitrate and sodium molybdate, respectively, versus NiMoO4The electrochemical performance of examples 1, 7 and 8 and examples 1, 9 and 10, respectively, illustrate that the reaction temperature and reaction time also affect the NiMoO to some extent4The electrochemical performance of (2). NiMoO in examples 3 to 104The electrochemical performance of (a) is inferior to that of example 1.
The foregoing embodiments and description have been provided to illustrate the principles and preferred embodiments of the invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. High-capacity NiMoO for battery anode material4The preparation method of the energy storage material is characterized by comprising the following steps: the method comprises the steps of synthesizing nickel metal organic framework Ni-MOF through a first hydrothermal reaction by taking organic acid and a nickel source as precursors, N-N-Dimethylformamide (DMF) as a solvent and foamed nickel as a substrate; then putting the obtained Ni-MOF sample into a reaction kettle filled with mixed precursor liquid consisting of polyvinylpyrrolidone (PVP), a nickel source, a molybdenum source and deionized water, carrying out secondary hydrothermal reaction, washing with distilled water, and drying to obtain the NiMoO4An energy storage material.
2. The method of claim 1, wherein: the concentration of the organic acid is 0.05mol L-1The organic acid is one or a mixture of more of terephthalic acid, trimesic acid and phthalic acid.
3. The method of claim 2, wherein: the organic acid is terephthalic acid.
4. The method of claim 1, wherein: the nickel source is one or a mixture of nickel nitrate, nickel chloride and nickel sulfate.
5. The method of claim 4, wherein: the nickel source is nickel nitrate.
6. The method of claim 1, wherein: the concentration of the molybdenum source is 0.05-0.15 mol L-1The molybdenum source is one or a mixture of sodium molybdate and ammonium molybdate.
7. The method of claim 1, wherein: the temperature of the first hydrothermal reaction is 100 ℃, and the time is 8 hours; the temperature of the second hydrothermal reaction is 120-180 ℃, and the hydrothermal reaction lasts for 3-9 h; the drying temperature and time are respectively 60 ℃ and 10 h.
8. The method of claim 1, wherein: the concentration of the nickel source in the first hydrothermal reaction is 0.05mol L-1(ii) a The concentration of the nickel source in the precursor solution of the second hydrothermal reaction is 0.05-0.15 mol L-1
9. The method of claim 8, wherein: the concentration of the nickel source in the first hydrothermal reaction is 0.05mol L-1(ii) a The concentration of the nickel source in the precursor solution of the second hydrothermal reaction is 0.1mol L-1
10. The method according to any one of claims 1 to 9, comprising in particular the steps of:
s1), sequentially immersing the foamed nickel in acetone and 3mol L-1Ultrasonic cleaning with hydrochloric acid and ethanol for 10min, 5min and 5min, respectively, and placing in a hydrothermal reaction kettle;
s2), the concentration is 0.05mol L-1And 0.05mol L of an organic acid-1Dissolving the nickel source in a DMF solvent, stirring until the nickel source is completely dissolved, pouring the mixture into the reaction kettle in the step S1), reacting for 8 hours in an oven at 100 ℃, taking out, washing by distilled water, and drying at 60 ℃ to synthesize a Ni-MOF sample;
s3), placing the Ni-MOF sample in a container with the concentration of 1.5mmol L-1The PVP and the concentration of the PVP is 0.05-0.15 mol L-1The concentration of the nickel source is 0.05-0.15 mol L-1Carrying out a secondary hydrothermal reaction in a reaction kettle of a mixed precursor solution consisting of a molybdenum source and deionized water, washing with distilled water, and drying at 60 ℃ for 10h to obtain the NiMoO4An energy storage material.
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CN111009421A (en) * 2019-11-22 2020-04-14 中国矿业大学 Lamellar bimetallic organic framework compound and preparation method and application thereof
CN111146442A (en) * 2019-12-27 2020-05-12 东华大学 High-performance nickel-zinc battery positive electrode material CoXNi1-XMoO4And their preparation and use
CN113929105B (en) * 2021-09-01 2023-11-17 安徽理工大学 Preparation method of metal organic framework derived nickel silicate
CN115295317B (en) * 2022-06-28 2023-07-07 电子科技大学长三角研究院(湖州) Preparation method of in-situ growth electrode material

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CN109133193A (en) * 2018-08-13 2019-01-04 浙江工业大学 A method of metal hydroxides multilevel structure is prepared using the derivative bimetallic oxide template of MOF
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CN109317205A (en) * 2018-11-12 2019-02-12 中国科学技术大学 Ferronickel Base Metal organic framework materials rich in cyano vacancy, preparation method and applications

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